Halogenated phenolic germicidal compositions containing terpene color stabilizers

ABSTRACT

Aqueous solutions containing halogenated phenolic germicidal compositions are stabilized against color change on exposure to light by providing in the solutions an effective amount of a discoloration inhibitor selected from the group consisting of alpha-phellandrene, allo ocimene, ocimene, terpinolene, myrcene, isoprene, rosin, tall oil, myrcene hydrate, and abietic acid. The solutions may also contain up to 35 percent of a detergent and other conventional detergent adjuvants.

United States Patent Carroll et al.

1 51 June 20, 1972 HALOGENATED PHENOLIC GERMICIDAL COMPOSITIONSCONTAINING TERPENE COLOR STABILIZERS Francis Emery Carroll, Wyckofi;Walter Charles Seebold, Westwood, both of NJ.

Lever Brothers Company, New York, N.Y.

Filed: Aug. 17, 1970 Appl. No.: 64,623

Inventors:

Assignee:

Related US. Application Data Continuation-in-part of Ser. No. 673,264,Oct. 6, 1967, abandoned.

US. Cl ..424/174, 252/106, 252/107, 424/195, 424/230, 424/317, 424/347,424/355, 424/356 Int. Cl ..A01n 9/30, C1 1d 3/48, Cl 1d 9/50 Field ofSearch ..424/174, 195, 59, 60, 230, 424/317, 347, 355, 356; 252/106,107; 260/489, 652.5

Primary E.\'aminerAlbert T. Meyers Assistant Examiner-Leonard SchenkmanAttorney-Brumbaugh, Graves, Donohue & Raymond [57] ABSTRACT Aqueoussolutions containing halogenated phenolic germicidal compositions arestabilized against color change on exposure to light by providing in thesolutions an effective amount of a discoloration inhibitor selected fromthe group consisting of alpha-phellandrene, allo ocimene, ocimene.terpinolene, myrcene, isoprene, rosin, tall oil, myrcene hydrate, andabietic acid. The solutions may also contain up to 35 percent of adetergent and other conventional detergent adjuvants.

22 Claims, N0 Drawings I HALOGENATED PIIENOLIC GERMICIDAL COMPOSITIONSCONTAINING TERPENE COLOR S'IABILIZERS This application is acontinuation-in-part of application, Ser. No. 673,264, filed Oct. 6,I967, now abandoned.

The present invention relates to aqueous solutions containinghalogenated phenolic germicidal compositions which have improvedstability against discoloration by light.

Aqueous solutions containing halogenated phenolic germicidalcompositions, such as tribromosalicylanilide (TBS),dibromosalicylanilide (DB8), and hexachlorophene, change color onexposure to sunlight, actinic light and even artificial light forprolonged periods of time. The freshly made aqueous compositions arecolorless or slightly yellowish, but change to a dark amber within avery few hours of exposure to light. Special precautions are thusnecessary in the manufacture, packaging and distribution of thesegermicidal solutions to insure that they do not become exposed to lightand undergo undesirable color change.

One prior art attempt to improve the color stability of germicidalcompositions is by the incorporation therein of an inorganic sulfite.While such compositions have improved stability against discoloration,the inorganic sulfite imparts an undesirable sour odor which consumersdislike. More importantly, where these germicidal liquid compositionscontaining sulfite are packaged and sold in resilient containers, it hasbeen noted that the containers are subject to significant collapse orpaneling of their resilient walls. This is thought to be occasioned bythe removal of oxygenfrom the head space of the resilient container dueto the presence of the inorganic sulfite reducing agent.

It is accordingly an object of the present invention to provide anaqueous germicidal composition based on halogenated phenolic germicides,which solutions have improved stability to discoloration by light andwhich, at the same time, are free of the disadvantages of the prior artset forth above. It is a further object to provide aqueous germicidaldetergent compositions having the same advantages.

It has now been found that aqueous solutions of halogenated phenolicgermicides can be significantly stabilized against color change in thepresence of light by incorporating in such compositions, as stabilizers,a compound selected from the group consisting of alpha-phellandrene,allo ocimene, ocimene, terpinolene, myrcene, isoprene, rosin, tall oil,myrcene hydrate and abietic acid. Of these materials, the most effectiveare alpha-phellandrene, allo ocimene, ocimene, terpinolene and myrcene.The isoprene and abietic acid are somewhat less effective but,nevertheless, retard color development to a significant extent.

These compositions are terpenes and are generally representative of manyof the classes of known terpenes. For

' example, the ocimene and myrcene are acyclic monoterpeand providesresults similar to those obtained with abietic acid itself. An analysisof a typical wood rosin is as follows:

Fraction Sinpine, a commercially available mixture of terpenes, providesexcellent results. The approximate composition of Sinpine is as follows:

Terpinolene 10% oz pinene 15% a terpinene 20% Dipentene 20% Cineol 10%Camphene 15% 'y terpinene 5% Unidentified 5% Total: [00% Mugol andMyrcenol are trade names for mixtures of terpene alcohols which havebeen found to provide stabilizing activity' equivalent to that obtainedwith isoprene and abietic acid. The structure of Myrcenol is given inU.S. Pat. No. 3,075,003; it is called myrcene hydrate in line 43, column2. Mugol is the compound shown in U.S. Pat. No. 2,867,688, top of column3, as a mixture of 3 isomers: viz., cis and trans at the indicateddouble bond in the structure in line 15, the other double bond beingtrans, and in the structure in line 19 the double bond being trans. Themixture consists of about 50 percent of the cis-trans mixture in ratioof 1:2 and the balance being the structure in line 19.

Tall oil, a distilled product containing a high percentage of rosinacids also provides results approximating those obtained by abieticacid. Tall oil has the following analysis:

tain phytosterols, lignins,

mercaptans and higher alcohols 0n the other hand, many terpenes andrelated compounds have been found to be completely ineffective. Thefollowing compounds gave no color stabilizing effect: linalyl acetate,geranyl acetate, limonene, alpha pinene, beta pinene, terpinyl acetate,neryl acetate, alpha-terpineol, quinone, methyl eugenol, camphene, amylcinnamic aldehyde, laevo carvone, pipertone, colchicine, beta ionone andmenthanyl acetate terpenes.

The aqueous germicidal solutions of the present invention usuallycontain a solubilizer. The brominated salicylanilides are highlyinsoluble in water. The potassium salt of tribromosalicylanilide isslightly soluble in water at room temperature. A solvent for thegermicides is required which is also miscible in water. Water admixedwith a lower aliphatic monohydric or polyhydric alcohol, such asmethanol, ethanol, propanol or glycol is useful. Solvents of this naturealso include acetone, xylene sulfonate and n-propyl alcohol. Incompositions containing mixed detergent active materials, the germicidesmay be dissolved in one of these materials. For example, in compositionscontaining lauric diethanolamide as a suds booster, the germicide can bedissolved in the amide prior to formulating the balance of thecomposition. 7

The halogenated phenolic germicides used to make the color stabilizedcompositions of this invention should be present in germicidal effectiveamounts. The appropriate amount will vary, depending upon the nature ofthe solution, and generally will range from 0.1 percent to about 4percent by weight. A preferred amount is about 0.4 percent by weight ofthe total composition.

The halogenated phenolic germicides are well known conventionalmaterials, representative examples of which include the normal andalkali metal salt forms of 4'-monobromosalicylanilide,5-monobromosalicylanilide, 4',5-dibromosalicylanilide,3,5-dibromosalicylanilide, 3,4',5-tribromosalicylanilide,3,4',S-trichlorosalicylanilide, 3',4,5-trichlorosalicylanilide,3,3',4',5-tetrachlorosalicylanilide, trichlorocarbanilide, andhexachlorophene or 2,2-dihydroxy, 3,5,6,3',5' ,6'-hexachlorodiphenylmethane. Of these the preferred halogenated phenolic germicides arehexachlorophene and the normal and equivalent alkali metal salt forms of3,4',5- tribromosalicylanilide and 4',5-dibromosalicylanilide as well asmixtures thereof containing at least about 50 percent by weight of3,4',5-tribromosalicylanilide. Other halogenated phenolic germicideswhich discolor on exposure to light and which may be stabilized by theaddition of terpene compositions according to this invention include2,4,6- trichlorophenol, tetrachlorophenol, 4-chloro-2-cyclopentylphenol,sodium pentachlorophenate, p-chloro-m-cresol, bithionol or 2,2'-thiobis(4,6-dichlorophenol), 3-[2-hydroxy-3,5-dichlorophenyl1-5,7-dichlorocoumaran, o-benzyl-pchlorophenol and4,6-dibromocresol.

In accordance with one preferred embodiment of the invention, theaqueous halogenated germicide solution contains a detergent.fAmmoniumalkyl aryl sulfonate is an example of a suitable detergent and may beused alone or in combination with an ammonium C -C alcohol 3E0 sulfateand lauric diethanolamide. Other compatible detergents generally knownin the art may be employed. Typical of such detergents are anionic,cationic or nonionic non-soap detergents and water-soluble fatty acidsoaps. Furthermore, other detergent adjuvants, such asinorganic-detergents, inorganic builder salts, sequestering agents,hydrotropes, opacifiers, perfumes, soilsuspending agents, opticalbrighteners, colorants, and abrasive particles maybe used. Suchmaterials are conventional materials for the formulation of aqueousdetergent compositions and have been fully described in the technicaland patent literature, for example, in Soaps and Detergents" by Thomssenand McCutcheon and Encyclopedia of Chemical Technology by Kirk andOthmer.

The stabilizers of this invention are used in an amount sufficient toretard or prevent discoloration of the aqueous germicidal compositions.Generally speaking, amounts ranging from 0.25'to 1 percent have beeneffective with germicide levels of 0.4 percent. In addition, stabilizerlevels ranging from 1 to 5 percent have been useful with a 4 percentlevel of germicide. Reverting to specific examples, an aqueous solutioncontaining TBS as the germicide at a level of 0.4 percent is completelystabilized for 72 hours exposure to light by the use ofalpha-phellandrene at a level ranging from 0.25 to 1 percent.

With an aqueous solution containing 0.4 percent TBS, a level of myrceneranging from 0.5 to 1 percent was an effective stabilizer, while withthe same TBS solution, ocimene was effective over a range of 0.25 to 1percent, and abietic acid was partially effective over a range of 0.1 to0.5 percent.

The following examples serve to illustrate the invention previouslydisclosed and are not intended to limit it in any way. All percentagesare by weight unless otherwise indicated.

EXAMPLE 1 Ingredients by Weight TBS 0.4 Acetone 93.6 Water misc. 5.0Stabilizer 1.0 Total: 100.0

After preparation, samples of the various liquids containing the variouscolor stabilizers were stored in glass bottles on a roof so as toprovide constant exposure to light during the daytime hours. The colorof the liquids was graded at the time the liquids were made and atvarious intervals thereafter. The following legend was used to evaluatethe compositions in conducting the visual color grading tests:

0 Colorless to slight yellow tint l Very slightly yellow 2 Slightlyyellow to slightly amber 3 Yellow to medium amber 4 Amber Table 1 belowgives the values assigned to the compound initially and after 2 hours,15 hours, and 106 hours of exposure to daylight. Liquids having a colorgrading of 3 or more are considered unsatisfactory with respect to colorstability.

TABLE 1 Visual Color Gradings of Liquids After Exposure to Daylight forStabilizer 0 Hrs. 2 Hrs. 15 Hrs. 106 Hrs.

Terpinolene 0 l 2 l Alpha-phellandrene 0 0 0 0 Allo ocimene 0 0 0 0Sinpine' 0 1-2 3 1-2 Sinpine (redistilled) 0 1-2 2 l Ocimene 0 0 0 0Myrcene 0 0 2 l-2 "Sinpine is a mixture of terpenes supplied byGivaudan-Delawanna lnc.

Abietic acid l 1-2 2 2 Rosin WW 0 1-2 2 1-2 None 0 2 4 4 "About rosinacids and 10% nonacids.

EXAMPLE 11 A liquid composition was prepared according to the inventionto contain 0.4 percent TBS in acetone and water with no adjustment ofthe pH taking place after the addition of the color stabilizers. Theseliquids had a pH within the range of 3-3.5. Their composition was asfollows:

Ingredients by Weight TBS 0.4 Acetone 79.6 Stabilizer 1.0 Water andMisc. 19.0 Total: 100.0

The effect of light on the color of the above liquid containing variousstabilizers is given in Table 2 below. After 72 hours, the initiallycolorless liquids without stabilizers had changed to a yellow color. Theother compounds prevented a color change.

TABLE 2 Visual Color Gradings of Liquids After Exposure to Light for 0Hrs. 72 Hrs.

Stabilizer Allo ocimene Abietic acid Rosin WW Myrcene OcimeneAlpha-phellandrene Mugol Sinpine None U OOOOOOO Described in Example I Aterpene alcohol, supplied by International Flavors and Fragrances, lnc.

EXAMPLE in Aqueous germicidal compositions were prepared containing 0.4percent TBS in alcohol and water and adjusted to a pH of I03 withpotassium hydroxide. The composition of the germicidal liquid was asfollows:

ingredients by Weight TBS 0.4

N-propyl alcohol 50.0

KOH (50%) 0.125

Stabilizer 1.0

Water and misc. 48.475 100.000

Total:

Table 3 below gives the visual color gradings made when the solutionswere initially prepared, and after 72 hours of exposure to light.

TABLE 3 Visual Color Gradings of Liquids After Exposure to Light forStabilizer Hrs. 72 Hrs.

Abietic acid 0 0 Rosin WW 0 0 Allo ocimene 0 0 Sinpine 0 0 Pipertone 0 4None 0 4 Legend 0 colorless to slight yellow tint 4 amber The controlliquid containing no stabilizer and the liquid containing pipertone wereamber. The remaining liquids ranged from colorless to a slight yellowtint.

EXAMPLE lV Gcrmicidal liquid formulations containing 4 percent TBS andvarious levels of alpha-phellandrene were tested for light stability.The composition of the liquids were as follows:

ingredients I: by Weight TBS 4.0 Acetone 86-9l Stabilizer 0-5 Water 5.0

The compositions had a pH within the range of 2.3-2.7.

Table 4 gives the visual color gradings obtained. A reading of 0indicates a colorless liquid, whereas a reading of 3 designates a yellowto medium amber liquid.

A germicidal liquid formulation containing 1 percent TBS and 1 percentof various color stabilizers was tested for light stability. Thecomposition of the liquid was as follows:

Ingredients b by Weight TBS l.O Acetone 93.0 Water 5.0 Stabilizer l.0

Total: 100.0 Pb 6.6

Table 5 below shows the results of the tests. In the visual colorgradings, 0 is colorless, 2 is slightly yellow to slightly amber, and 4is amber.

TABLE 5 Visual Color Gradings of Liquids After Exposure to Daylight forStabilizer 0 Hrs. 106 Hrs.

Allo ocimene 0 2 Alpha-phellandrene 0 2 None 0 4 The above demonstratesthat a germicidal liquid containing 1 percent TBS changes from acolorless liquid to an amber liquid when exposed to daylight. The colorbegan to develop almost immediately on exposure to light and the liquidwas noticeably colored in about 2 hours. Liquids containing thestabilizers were stabilized as a slight yellow liquid as compared to theamber or reddish brown color with the control liquid.

EXAMPLE VI Germicidal liquids containing hexachlorophene, both with andwithout color stabilizers, were tested for light stability. Thecomposition of the germicidal liquids was as follows:

ingredients 1: by Weight Hexachlorophene 0.4 Aeetoae 54.0 Water 44.6Stabilizer l .0 Total 100.0

Table 6 below gives the visual color gradings obtained by using variousstabilizers in the above germicidal liquid compositions. In thegradings, 0 indicates a colorless solution, 3 a yellow to medium amberand 4 designates amber.

TABLE6 3 Visual Color Gradings of Liquids After Exposure to Daylight forS Stabilizer Hrs. 336 Hrs.

Alpha-phellandrene 0 0 Allo oeimene 0 0 Benzene .0 4 l0 Laevo carvone 03 None 0 4 The liquids containing hexachlorophene changed from colorlessto amber on exposure to light. Alpha-phellandrene and allo oeimeneprevented discoloration of the liquid. Benzene and laevo carvone wereineffective as color stabilizers.

EXAMPLE Vll Germicidal-liquid detergent formulations containing 0.4percent hexachlorophene and l0 percent dodecylbenzene sulfonate,together with various color stabilizers were prepared. The compositionshad the following formula, with a pH of 6-7.5:

Ingredients I: by Weight NH Ucane l2 sulfonate l0.0 Hexachlorophene 0.4Acetone 46.0 Water 42.6 Stabilizer l .0 Total: 100.0

Color gradings of the solutions were made on the following basis: 0colorless to a slightly yellow tint; l slightly yellow, 40 and 4 amber.

Table 7 below summarizes the results obtained.

TABLE 7 Visual Color Gradings of Liquids After Exposure to Daylight forStabilizer 0 Hrs. 336 Hrs.

Alpha-phellandrene 0-l 0 Allo ocimene O-l 0 Benzene 0-l 4 Laevo carvone0-1 4 None 0-] 4 The detergent formulations containing hexachlorophenechanged from a colorless liquid to an amber liquid on exposure todaylight. Alpha-phellandrene and allo ocimene The liquids were preparedby dissolving the detergent and TBS in acetone and water. The colorstabilizer was added last and the pH of the liquid was adjusted towithin the range of 6-7.5 with either sodium or ammonium hydroxide orsulfuric acid. The acetone was used to dissolve the TBS which isinsoluble in water. Samples of the liquid containing various organiccomponents undergoing evaluation as stabilizers were stored on a roof inglass bottles for exposure to light.

Table 8 below gives the visual color gradings for these substances aftervarious periods of exposure to daylight. 0 is colorless to a slightlyyellow tinted solution. 1 indicates very slightly yellow. 2 indicatesslightly yellow to slightly amber, and 3 is yellow to medium amber.

' TABLE 8 Visual Color Gradings of Liquids After Exposure to Daylightfor Stabilizer 0 Hrs. 2 Hrs. 35 Hrs. 336 Hrs.

Linalyl acetate Terpinyl Neryl acetate Terpinolene Beta pinene Betaionone Methyl eugenol Mugol Myrcenol Methanyl acetate terpenesAlpha-phellandrene Allo oeimene Sinpine Sinpine (redistilled) OcimeneMyrcene Abietic acid Rosin WW Tall oil fatty acid lsomerized linoleicacid None CG OO-OOO QOOO OOOOOOOOO BIN NONOOO OOON -ONNNONNN The liquiddetergent containing no additive changed from a colorless liquid to ayellow or slightly amber liquid in 2 hours and to a yellow to mediumamber liquid in 35 hours. The liquids containing terpinolene, Mugol,alpha-phellandrene, allo oeimene, Sinpine, oeimene, myrcene and Rosin WWwere graded 0 after 336 hours of exposure to light.

EXAMPLE [X Germicidal aqueous detergent compositions were preparedcontaining 0.4 percent TBS, 10 percent ammonium dodecylbenzene sulfonateand 1 percent of various organic compounds as color stabilizers. Afterstoring these solutions for a period of time, they were graded accordingto the following visual evaluations:

Mugol 2 l-2 2 Myrcenol 0 2 1-2 2 Alpha-phellandrene 0 0 0 0 Allo ocimene0 0 0 0 Sinpine 0 2 1-2 1 Ocimene 0 2 1-2 1 Myrcene 0 2 0 l Abietic acid1 2 2 2 Rosin WW 0 1 1-2 1 None 0 2 3 4 The data show that the liquidcontaining no stabilizer changed from a colorless liquid to one having aslight yellow to a slight amber tint in 2 hours, and to an amber liquidafter 280 hours exposure to light. The liquids containingalpha-phellandrene and allo ocimene were colorless liquids after 280hours of exposure to light. The other stabilizers were effective but toa lesser extent.

EXAMPLE X Germicidal liquid detergents containing 0.4 percent TBS,percent lauric diethanolamide and 1 percent of various organic compoundsas color inhibitors were prepared and were visually evaluated accordingto the following table:

0 Colorless to light yellow tint l very slightly yellow 2 slightlyyellow to slightly amber 3 yellow to medium amber Table 10 below givesthe results of these experiments.

TABLE 10 Visual Color Gradings of Liquids After Exposure to Daylight forAdditive 0 Hrs. 2 Hrs. 35 Hrs. 336 Hrs.

Terpinolene Beta pinene Mugol Myrcenol Alpha-phellandrene Allo ocimeneSinpine Sinpine (redistilled) Ocimene Myrcene Abietic acid Rosin WW Talloil fatty acid None OOO-OOOOOOOOOO WwNNNONNOONNNN U NNNCQOMOONUNN--OOOOOOO The liquids containing terpinolene, alpha-phellandrene, alloocimene, sinpine, ocimene, and myrcene were colorless liquids after 336hours of exposure to light, whereas the control changed to a yellow to amedium amber liquid after 2 hours.

EXAMPLE XI A germicidal liquid detergent composition was prepared tohave the following formula:

Ingredients by Weight NH. dodecylbenzene sulfonate (Ucane 12) NH, Alfol1412 SEC sulfate Lauric diethariolamide NH. xylene sulfonate TABS Waterand misc.

Stabilizer Total:

The liquids were prepared by dissolving the TBS in lauric diethanolamideand then adding this mixture to an aqueous solution of the twosulfonates and the sulfate. The color stabilizer was then added and thepH of the material adjusted to 6-7 by the addition of sulfuric acid. Theliquids were stored for varying periods of time and then evaluatedaccording to the following:

0 colorless to slightly yellow tint l very slightly yellow to veryslightly amber 2 slightly yellow to slightly amber 3 yellow to mediumamber 4 amber 5 dark amber Table 11 below gives the results of theseexperiments.

The control liquid containing no additive changed to a medium ambercolor in 2 hours and to a dark amber after 30 hours of exposure tolight. The liquids containing allo ocimene, redistilled Sinpine,terpinolene and ocimene maintained a very slight yellow to a slightamber color after 194 hours of exposure to light.

EXAMPLE X" A number of germicidal liquid detergents having thecomposition given in Example Xl were prepared containing 0.4 percent TBSand varying levels of alpha-phellandrene. Table 12 below summarizes theresults of the visual color evaluations of this series of tests, usingthe grading system of Example X1.

TABLE 12 Visual Color Grade of Liquids Exposed to Light for I:Alpha-phellandrene 0 Hrs. 72 Hrs.

EXAMPLE XII! The effect of varying the levels of myrcene in thecomposition of Example X1 is given in the following table. The visualcolor grading system of Example X1 was used.

TABLE 13 Visual Color Grade of Liquids Exposed to Light for I: Myrcene 0Hrs. 72 Hrs.

.1. 12 0.5 1 l TABLE l7 1.0 l l EXAMPLE XIV Visual Color Grading AfterExposure to Light for The effect of varying the oclmene levels in thegermicidal Germicidal Composition composition of Example Xi is given inthe following table. The A visual color grading system of Example Xl wasused.

0 0 0 TABLE l4 36 l 0 60 2 0 84 3 0 120 4 0 Visual Color Grade ofLiquids I44 4 0 Exposed to Light for I68 4 0 Ocimene 0 Hrs. 72 Hrs. 5204 5 0 g l l g 7 EXAMPLE XVlll I l 015 1 1 Two germicidal solutionscontaining l percent 1 i tetrachlorophenol and 75 percent ethanol wereprepared. The first solution, B, simply contained a balance of waterwhile the second solution, B, contained in addition 1.0 percent alloEXAM LE XV ocimene. Thetwo solutions were visually color graded afterThe effect of varying the Rosin WW levels in the germicidal exposure mham accordm to the following legend:

0 colorless composition of Example XI is given in the following table.The visual color grading system of EXam le XI was used 1 very light p 2light violet TABLE 15 3 medium violet 4 --dark violet 5 very dark violetvisual Color Grade of Liquid. The results of this experiment arereported below in Table Exposed to Light for l8. k Rosin WW 0 Hrs. 72Hrs.

TABLE 18 0.1 l 5 0.15 l 5 Visual Color Grading After 0.20 l l-2 Exposureto Light for 0.25 l l-2 Germicidal Composition 0.5 l l-Z Hours B B 1.0 ll-2 4 26 0 0 l 0 EXAMPLE XVI 6o 2 o The effect of varying the abieticacid levels in the germicidal n i g composition of Example Xl is givenin the following table. The 5 1 g 0 visual color grading system ofExample XI was used. 3 5 0 i 204 5 0 TABLE 16 so EXAMPLE XIX VisualSolor Gaadfe of Liquids Two gennicidal solutions containing LOpercent4-chloro- W l l Z-cycIopentylphenol and 75 percent ethanol wereprepared. ADM": 0 72 The first solution, C, simply contained a balanceof water while the second solution, C, contained in addition 1.0 per- 0l 5 5 5 cent allo ocimene. The two solutions were visually color 3graded after exposure to light according to the following 0125 1 1-2 0.5l [-2 0 trace yellow 1 slight yellow 0 2 light amber EXAMPLE Table 19gives the results of this experiment: Two gennicidal solutionscontaining 1.0 percent 2,4,6- TABLE 9 trichlorophenol and 75 percentethanol were prepared. The first solution, A, simply contained a balanceof water while the second solution, A, contained in addition 1.0 percentallo ocimene. The two solutions were visually color graded after gi t sggg'fi'al exposure to light according to the following legend: PoGcmicidfl composition 0 colorless Hours C C' l light pinkish violet 2medium pinkish violet o o 0 v 3 medium reddish violet 35 o o 4 darkreddish violet 60 l l 5 very dark reddish violet g 8 The results of thisexperiment are reported below .in Table 9 I 0 17: m z o EXAMPLE XX Twogermicidal solutions containing 1.0 percent sodium pentachlorophenateand 75 percent ethanol were prepared. The first solution, D, simplycontained a balance of water while the second solution, D, contained inaddition 1 percent allo ocimene. The two solutions were visually colorgraded after exposure to light according to the following legend:

0 slight yellow 1 medium brown 2 dark brown 3 very dark brown 4 verydark reddish brown The results of this experiment are reported in TableTABLE 20 Visual Color Grading After Exposure to Light for GermicidalComposition Hours D EXAMPLE XXI Two germicidal solutions containing 1.0percent p-chlorom-cresol and 75 percent ethanol were prepared. The firstsolution, E, simply contained a balance of water while the secondsolution, B, contained in addition 1.0 percent allo ocimene. The twosolutions were visually color graded after exposure to light accordingto the following legend:

0 colorless l slightly pink 2 medium pink The results of this experimentare reported in Table 2 l:

Two germicidal solutions containing 1.0 percent 2,2-thiobis(4,6-dichlorophenol) and 75 percent ethanol were prepared. Thefirst solution, F, simply contained a balance of water while the secondsolution, F, contained in addition 1 percent allo ocimene. The twosolutions were visually colored graded after exposure to light accordingto the following legend:

0 colorless l medium yellow 2 medium amber 3 reddish amber 4 mediumreddish amber 5 dark amber The results of this experiment are reportedin Table 22:

TABLE 22 Visual Color GradingAfter Exposure to Light for GermicidalComposition Hours F EXAMPLE XXlll Two germicidal solutions containing1.0 percent 3',4',5- trichlorosalicylanilide, to percent lauricdiethanolamide and 75 percent ethanol were prepared. The first solution,G, simply contained a balance of water while the second solution, G,contained in addition 1 percent allo ocimene. The two solutions werevisually color graded after exposure to light ac-' cording to thefollowing legend:

0 colorless I l dark yellow 2 dark amber 3 very'dark amber 4 darkreddish orange 5 very dark orange The results of this experiment arereported in Table 23:

TABLE 23 Visual Color Grading After Exposure to Light for GermicidalComposition Hours G G Ln b oa-0 OOOOQOOO EXAMPLE XXIV Two germicidalsolutions containing 1.0 percent 3-[2-hydroxy-3,S-dichlorophenyl]-5,7-dichlorocoumaran and 75 percent ethanolwere prepared. The first solution, H, simply contained a balance ofwater while the second solution, H, contained in addition 1.0 percentallo ocimene. The two solutions were visually color graded afterexposure to light according to the following legend:

0 slight lemon yellow 1 medium amber 2 brownish amber 3 medium brown 4medium greenish brown The results of this experiment are reported inTable 24:

TABLE 24 Visual Color Grading After Exposure to Light For I GermicidalComposition Hours H H EXAMPLE XXV Two germicidal solutions containing1.0 percent o-benzyl-pchlorophenol and 75 percent ethanol were prepared.The first solution, I, simply contained a balance of water while thesecond solution, 1', contained in addition 1.0 percent allo ocimene. Thetwo solutions were visually color graded after 2,4,6-trichloroplienol .05 .0 5 .0 5.0 Ethanol 75.0 75.0 75.0 75.0 Allo ocimene L0 3.0 5.0 Water20.0 19.0 l7.0 l5.0

These solutions were visually color graded at varying time intervalsduring a 228 hour light exposure period according to the followinglegend:

0 colorless l slightly yellow 2 light reddish purple 3 dark reddishpurple exposure to light according to the following legend: 4 mediumpinkish red 0 colorless 5 medium crimson 1 very light pink 6 d k 2 darkp very ar crimson I The results of this experiment are reported in Table27: 3 orange pink 4 medium orange pink TABLE 27 5 light amber 6 mediumamber Table gives the results of this experiment: visual color GndinAft" Exposure to Light for TABLE 25 25 Germicidal Composition Hours M iVisual Color Grading After 0 0 0 0 0 Exposure to Light for 35 2 0 0 0Germicidal Composition 34 3 0 0 0 Hours l l' 144 4 i l 0 I68 5 l l 0 I925 l l 0 0 0 0 228 6 l l 0 36 l 0 60 2 0 84 3 0 120 4 0 EXAMPLE XXVI]! g8 Four germicidal solutions having the following composi- 204 6 o tionswere prepared:

40 Germicidal Composition: N% N'% N'% N'% EXAMPLE XXVI Two germicidalsolutions containing 1.0 percent 4,6- 2,4,6-trichlorophenol 1.0 1.0 1.01.0 dibromocresol and 75 percent ethanol were prepared. The 750 751) 75first solution, .I, simply contained a balance of water while the a 0J0ater 24.0 23.9 23.75 23.50 second solution, J contained in addition 1percent allo ocimene. Two solutions were visually color graded afterexposure to light according to the following legend:

0 colorless l medium pink 2 medium red 3 medium orange red 4 mediumorange Table 26 shows the results of this experiment:

TABLE 26 5 5 Visual Color Grading After Exposure to Light for GermicidalComposition Hours J .I'

0 0 0 36 l l 60 2 0 a4 3 0 l 20 3 0 I44 3 0 l 68 4 0 204 4 0 70 EXAMPLEXXVll Four germicidal solutions having the following compositions wereprepared:

Germicidal Composition MIi MW) M% M'% These solutions were visuallycolor graded at varying time intervals during a 228 hour light exposureperiod according to the following legend:

0 colorless l very light pinkish violet 2 medium reddish violet 3 lightreddish violet 4 dark reddish violet 5 very dark reddish violet Theresults of this experiment are reported in Table 28:

1. An aqueous germicidal Composition having improved stability againstdiscoloration by light which comprises an aqueous solution containingfrom about 0.1 percent to about 4 percent by weight of a halogenatedphenolic germicide susceptible to discoloration by light, and adiscoloration retarding amount of a discoloration inhibitor selectedfrom the group consisting of alpha-phellandrene, allo ocimene, ocimene,terpinolene, myrcene, myrcene hydrate, rosin, tall oil, isoprene andabietic acid.

2. An aqueous germicidal composition having improved stability againstdiscoloration by light which comprises an aqueous solution containingfrom about 0.1 percent to about 4 percent by weight of a halogenatedphenolic germicide selected from the group consisting of3,4',5-tribromosalicylanilide, 4,S-dibromosalicylanilide, andhexachlorophene, and a discoloration retarding amount of a discolorationinhibitor selected from the group consisting of alpha-phellandrene, alloacimene, ocimene, terpinolene, myrcene, myrcene hydrate, rosin, talloil, isoprene and abietic acid.

3. The composition according to claim 1 wherein the discolorationinhibitor is selected from the group consisting of alpha-phellandrene,allo ocimene, ocimene, terpinolene, and myrcene.

4. The composition according to claim 1 wherein the inhibitor is presentat a level of at least about 0.25 percent by weight.

5. The composition according to claim 1 wherein a solubilizer is alsopresent, said solubilizer being miscible in water and also a solvent forthe germicide.

6. The composition according to claim 1 which additionally contains from1 to 35 percent of a detergent.

7. The composition according to claim 1 wherein the halogenated phenolicgermicide is selected from the group consisting of tetrachlorophenol,4-chloro-2-cyclopentylphenol, sodium pentachlorophenate,p-chloro-m-cresol, 2,2'-thiobis(4,6-dichlorophenol),3',4,5-trichlorosalicylanilide,3-[2-hydroxy-3,S-dichlorophenyl]-$,7-dichlorocoumaran,o-benzyl-p-chlorophenol, 4,6-dibromocresol, and 2,4,6-trichlorophenol.

8. The composition according to claim 7 wherein the inhibitor is 1percent allo ocimene and the germicide is 1 percent tetrachlorophenol.

9. The composition according to claim 7 wherein the inhibitor is 1percent allo ocimene and the germicide is 1 percent 4-chloro-2-cyclopentylphenol.

10. The composition according to claim 7 wherein the inhibitor is 1percent allo ocimene and the germicide is 1 percent sodiumpentachlorophenate.

11. The composition according to claim 7 wherein the inhibitor is lpercent allo ocimene and the gennicide is l percent p-chloro-m-cresol.

12. The composition according to claim 7 wherein the inhibitor is 1percent allo ocimene and the germicide is 1 percent2,2'-thiobis(4,6-dichlorophenol).

13. The composition according to claim 7 wherein the inhibitor is 1percent allo ocimene and the germicide is 1 percent3-[2-hydroxy-3,5-dichlorophenyl]-5,7-dich|orocoumaran.

14. The composition according to claim 7 wherein the inhibitor is 1percent allo ocimene and the germicide is 1 percento-benzyl-p-chlorophenol.

15. The composition according to claim 7 wherein the inhibitor is 1percent allo ocimene and the germicide is l percent 4,6-dibromocresol.

16. The composition according to claim 7 wherein the inhibitor is 1percent allo ocimene and the germicide is 0.10 to 5 percent2,4,6-trichlorophenol.

17. An aqueous germicidal composition having improved stability againstdiscoloration by light which comprises from about 0.1 percent to about 4percent by weight of a halogenated phenolic germicide susceptible todiscoloration by light, water, a solubilizer which is miscible in waterand is also a solvent for the germicide, from about 1 percent to about35 percent of deter em, and a discoloration retarding amount of adiscoloration lll lbitor selected from the group consisting ofalpha-phellandrene, allo ocimene, ocimene, terpinolene, myrcene, myrcenehydrate, tall oil, isoprene and abietic acid.

18. An aqueous germicidal composition having improved stability againstdiscoloration by light which comprises from about 0.1 percent to about 4percent by weight of a halogenated phenolic germicide selected from thegroup consisting of 3,4,S-tribromosalicylanilide,4,5-dibromosalicylanilide, and hexachlorophene, water, a solubilizerwhich is miscible in water and is also a solvent for the germicide, fromabout 1 percent to about 35 percent of a detergent, and a discolorationretarding amount of a discoloration inhibitor selected from the groupconsisting of alpha-phellandrene, allo ocimene, ocimene, terpinolene,myrcene, myrcene hydrate, rosin, tall oil, isoprene and abietic acid.

19. The composition according to claim 17 wherein the inhibitor isalpha-phellandrene, and is present at a level of 0.25 to 1 percent andthe germicide is 3,4',5-tribromosalicylanilide, present at a level ofabout 0.4 percent.

20. A composition according to claim 17 wherein the germicide is3,4,5-tribromosalicylanilide, present at a level of 0.4 percent and theinhibitor is myrcene, present at a level of 0.5 to 1 percent.

21. The composition according to claim 17 wherein the germicide is3,4',S-tribromosalicylanilide, present at a level of 0.4 percent and theinhibitor is ocimene at a level of 0.25 to 1.0 percent.

22. The composition according to claim 17 wherein the germicide is3,4',S-tribromosalicylanilide, present at a level of 0.4 percent and theinhibitor is abietic acid, present at a level of 0.1 to 0.5 percent.

' 0 i i i i STATES PATENT @IEUFEQIE QE'HFKQATE CETN Patent No. 3,6715%Dated June 20, 1972 Inventor(s) Francis Emery Carroll et al.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Col. 1, line 68, "53" is misplaced; Col. 2, line 19, change "2,867,688"to 2,867,668 Col. 3, line change "a" to as -5 Col. line 3, change "alloocimene, and" to allo ocimene, ocimene, and g. 001. 5, line 8, change"Sinpine 0" to Sinpine 0 0 Col. 6, line 29, change "Ph" to pH Col. 7line' 70, change"Nhu" to NH Col. 8, line 26, change "Terpinyl" toTerpinyl acetate 5 Col. 9, line 67, change "TABS" to TBS Col.' 10,, line19, under 60 hrs "0 hrs" unaligned; Col. 10, lines 26-29, 30, 2 2"unaligned;

Col. 10 line 29, under 30 hrs unaligned; Col. 11, line 18, change"10.25" to 0 .25 --g Col. 12, line 72, under 0 Y change "1" to 0 Col.13, line 32, "0 .204" is unaligned and should be 20 Col. 15, line 63,under .1 change "1" to 0 --5 Col. 16, line M, "0.10 0.25 0.50"unaligned; Col. 16, line 70, "0" is unaligned; C01. 17 line 18, change"acimene" to ocimene Signed and sealed this 10th day of April 1973(SEAL) Attest:

EDWARD M.PLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents

2. An aqueous germicidal composition having improved stability againstdiscoloration by light which comprises an aqueous solution containingfrom about 0.1 percent to about 4 percent by weight of a halogenatedphenolic germicide selected from the group consisting of3,4'',5-tribromosalicylanilide, 4,5-dibromosalicylanilide, andhexachlorophene, and a discoloration retarding amount of a discolorationinhibitor selected from the group consisting of alpha-phellandrene, alloacimene, ocimene, terpinolene, myrcene, myrcene hydrate, rosin, talloil, isoprene and abietic acid.
 3. The composition according to claim 1wherein the discoloration inhibitor is selected from the groupconsisting of alpha-phellandrene, allo ocimene, ocimene, terpinolene,and myrcene.
 4. The composition according to claim 1 wherein theinhibitor is present at a level of at least about 0.25 percent byweight.
 5. The composition according to claim 1 wherein a solubilizer isalso present, said solubilizer being miscible in water and also asolvent for the germicide.
 6. The composition according to claim 1 whichadditionally contains from 1 to 35 percent of a detergent.
 7. Thecomposition according to claim 1 wherein the halogenated phenolicgermicide is selected from the group consisting of tetrachlorophenol,4-chloro-2-cyclopentylphenol, sodium pentachlorophenate,p-chloro-m-cresol, 2,2''-thiobis(4,6-dichlorophenol),3'',4'',5-trichlorosalicylanilide, 3-(2-hydroxy-3,5-dichlorophenyl)-5,7-dichlorocoumaran, o-benzyl-p-chlorophenol,4,6-dibromocresol, and 2,4,6-trichlorophenol.
 8. The compositionaccording to claim 7 wherein the inhibitor is 1 percent allo ocimene andthe germicide is 1 percent tetrachlorophenol.
 9. The compositionaccording to claim 7 wherein the inhibitor is 1 percent allo ocimene andthe germicide is 1 percent 4-chloro-2-cyclopentylphenol.
 10. Thecomposition according to claim 7 wherein the inhibitor is 1 percent alloocimene and the germicide is 1 percent sodium pentachlorophenate. 11.The composition according to claim 7 wherein the inhibitor is 1 percentallo ocimene and the germicide is 1 percent p-chloro-m-cresol.
 12. Thecomposition according to claim 7 wherein the inhibitor is 1 percent alloocimene and the germicide is 1 percent2,2''-thiobis(4,6-dichlorophenol).
 13. The composition according toclaim 7 wherein the inhibitor is 1 percent allo ocimene and thegermicide is 1 percent 3-(2-hydroxy-3,5-dichlorophenyl)-5,7-dichlorocoumaran.
 14. The composition according to claim 7 whereinthe inhibitor is 1 percent allo ocimene and the germicide is 1 percento-benzyl-p-chlorophenol.
 15. The composition according to claim 7wherein the inhibitor is 1 percent allo ocimene and the germicide is 1percent 4,6-dibromocresol.
 16. The composition according to claim 7wherein the inhibitor is 1 percent allo ocimene and the germicide is0.10 to 5 percent 2,4,6-trichlorophenol.
 17. An aqueous germicidalcomposition having improved stability against discoloration by lightwhich comprises from about 0.1 percent to about 4 percent by weight of ahalogenated phenolic germicide susceptible to discoloration by light,water, a solubilizer which is miscible in water and is also a solventfor the germicide, from about 1 percent to about 35 percent ofdetergent, and a discoloration retarding amount of a discolorationinhibitor selected from the group consisting of alpha-phellandrene, alloocimene, ocimene, terpinolene, myrcene, myrcene hydrate, tall oil,isoprene and abietic acid.
 18. An aqueous germicidal composition havingimproved stability against discoloration by light which comprises fromabout 0.1 percent to about 4 percent by weight of a halogenated phenolicgermicide selected from the group consisting of3,4'',5-tribromosalicylanilide, 4,5-dibromosalicylanilide, andhexachlorophene, water, a solubilizer which is miscible in water and isalso a solvent for the germicide, from about 1 percent to about 35percent of a detergent, and a discoloration retarding amount of adiscoloration inhibitor selected from the group consisting ofalpha-phellandrene, allo ocimene, ocimene, terpinolene, myrcene, myrcenehydrate, rosin, tall oil, isoprene and abietic acid.
 19. The compositionaccording to claim 17 wherein the inhibitor is alpha-phellandrene, andis present at a level of 0.25 to 1 percent and the germicide is3,4'',5-tribromosalicylanilide, present at a level of about 0.4 percent.20. A composition according to claim 17 wherein the germicide is3,4'',5-tribromosalicylanilide, present at a level of 0.4 percent andthe inhibitor is myrcene, present at a level of 0.5 to 1 percent. 21.The composition according to claim 17 wherein the germicide is3,4'',5-tribromosalicylanilide, present at a level of 0.4 percent andthe inhibitor is ocimene at a level of 0.25 to 1.0 percent.
 22. Thecomposition according to claim 17 wherein the germicide is3,4'',5-tribromosalicylanilide, present at a level of 0.4 percent andthe inhibitor is abietic acid, present at a level of 0.1 to 0.5 percent.